CN1993177A - Catalysts containing tungstate for the synthesis of alkylmercaptane and method for the production thereof - Google Patents

Catalysts containing tungstate for the synthesis of alkylmercaptane and method for the production thereof Download PDF

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Publication number
CN1993177A
CN1993177A CNA2005800261123A CN200580026112A CN1993177A CN 1993177 A CN1993177 A CN 1993177A CN A2005800261123 A CNA2005800261123 A CN A2005800261123A CN 200580026112 A CN200580026112 A CN 200580026112A CN 1993177 A CN1993177 A CN 1993177A
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catalyst
alkali metal
tungsten
tungstates
carrier material
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CN1993177B (en
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胡贝特·雷德林绍弗尔
克里斯托夫·韦克贝克
克劳斯·胡特马赫尔
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Evonik Operations GmbH
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Degussa GmbH
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
    • C07C319/08—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by replacement of hydroxy groups or etherified or esterified hydroxy groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention relates to a catalyst containing alkali tungstate for the synthesis of alkylmercaptanes from alkanols and hydrogen sulphide, in addition to a method for the production of said catalyst, wherein the molar ratio of alkali to tungstan is < 2:1.

Description

The Catalysts and its preparation method that contains tungstates that is used for synthesis of alkyl mercaptan
Technical field
The present invention relates to comprise catalyst and this Preparation of catalysts method of being used for of alkali tungstates by alkanol and hydrogen sulfide synthesis of alkyl mercaptan.
Background technology
In present patent application, term alkali metal should be understood alkali metal in the periodic table of elements that is meant combination in tungstates or at least two kinds of alkali-metal mixtures of combination.In this case, caesium only exists with the other element of alkali metal family.
Especially a kind of industrial important intermediate of methyl mercaptan for example, be used for the synthetic of methionine, and dimethyl sulfoxide (DMSO) and dimethyl sulfone is synthetic.At present, it is mainly prepared by reacting on the catalyst of being made up of aluminium oxide by methyl alcohol and hydrogen sulfide.The synthetic of methyl mercaptan carries out under the pressure of 300-500 ℃ temperature and 1-25 crust in gas phase usually.
Except that formed methyl mercaptan, this reactant mixture also comprises unreacted initiation material and accessory substance, as dimethyl sulfide and dimethyl ether, and is inert gasses in reaction environment, as methane, carbon monoxide, hydrogen and nitrogen.Formed methyl mercaptan is isolated from this reactant mixture.
For the economic benefit of this method, in the catalytic reaction of methyl alcohol and hydrogen sulfide generation methyl mercaptan, need the highest selectivity, as far as possible simply and at an easy rate from reactant mixture, to isolate methyl mercaptan.At this, in particular for the cooling reaction gas mixtures so that the energy demand of methyl mercaptan condensation constitutes big cost factor.
For improving activity and selectivity, usually potassium tungstate or wolframic acid caesium are mixed with aluminium oxide as carrier.In this case, be benchmark with the total catalyst weight, usually use this tungstates with the amount of 25 weight % at the most.Also realized active and optionally improvement by the mol ratio that improves hydrogen sulfide and methyl alcohol.Usually, the mol ratio of use 1 to 10.
Yet high mol ratio also means high excessive hydrogen sulfide and so a large amount of gas of needs circulation in reactant mixture.In order to reduce the required energy demand of this purpose, therefore the mol ratio of hydrogen sulfide and methyl alcohol should only depart from 1 a little.
United States Patent (USP) 2,820,062 relates to the preparation method of organic mercaptan, and wherein use by activated alumina and urge the catalyst of forming, with the catalyst weight benchmark, the potassium tungstate of this catalyst with 1.5-15 weight % mixed.Adopt this catalyst, being 400 ℃ in reaction temperature is 2 o'clock good activity and selectivity of acquisition with mol ratio.This piece United States Patent (USP) has been mentioned the multiple possibility of potassium tungstate being introduced aluminium oxide.For example, adopt dipping method, co-precipitation and pure mixing to it is said possible.For the economic benefit of methyl mercaptan synthetic method, do not mention the actual fabrication of this catalyst basically.
EP 0 832 687 B1 have described use wolframic acid caesium (Cs 2WO 4) replacement potassium tungstate (K 2WO 4) as the advantage of co-catalyst.For example, the activity of using the wolframic acid caesium to obtain to strengthen obtains good selectivity simultaneously.
The concentration of wolframic acid caesium increased to up to 40 weight % allow the selectivity of methyl mercaptan is increased to 92%, and activity disproportionately reduces.
According to conventional viewpoint, the catalyst that uses the ratio of alkali metal/tungsten to equal 2: 1 obtains best selective (people's such as A.V.mashkina React.Kinet.Catal.Lett., Vol.36, No.1,159-164 (1988).
Summary of the invention
The objective of the invention is to illustrate Catalysts and its preparation method, compare that the characteristics of this catalyst under the low mol ratio situation of hydrogen sulfide and methyl alcohol are improved activity and selectivity, and therefore realize the better economic benefit of this method with known catalyst.
This purpose comprises the realization of catalytic activity alkali tungstates by providing, this catalytic activity alkali tungstates comprises the alkali metal and the tungsten of combination, the mol ratio of alkali metal and tungsten＜2: 1 wherein, especially＜2: 1 to 0.9: 1, preferred 1.9: 1 to 1: 1, especially 1.6: 1 to 1: 1.
This oxidising composition can be used general formula A xWO yDescribe, wherein A is an alkali metal, and x＜2 are to 0.9, and y is 3.4 to＜4.
The alkali metal component of the combination of this tungstates can be made up of one or more elements of alkali metal family.In this case, caesium only combines existence with other alkali metal.
This catalyst comprises 8-45 weight %, 15-36 weight % especially, this tungstates of preferred＞25 to 36 weight %.Under the situation of the catalyst that applies, these ratios are based on the composition of this coating.
The oxidized compound of being made up of alkali metal and tungsten can directly be impregnated into carrier formed body (support body) upward (loaded catalyst).
Be in preparation under the situation of catalyst of extrudate or mechanograph form, mix with this oxidising composition dipping powder carrier or with this powder carrier, and subsequently the gained intermediate is reshaped (unsupported catalyst).When preparing the catalyst that applies, flood this powder carrier with the catalytic activity composition, then the gained mixture is coated on the preferred inert carrier nuclear with coating form.
The ratio range of alkali metal/tungsten is preferably＜and 1.9: 1 to 1: 1.Therefore, with according to prior art with wolframic acid caesium (Cs 2WO 4) or potassium tungstate (K 2WO 4) catalyst of dipping compares, and is used for the tungsten that the reaction of alkanol and hydrogen sulfide produces the catalyst of the present invention of alkyl hydrosulfide so comprises the hyperstoichiometry ratio.
It is found that compare with the special stoichiometric alkali tungstates that uses in the prior art, more a high proportion of tungstates gives catalyst improved activity on the preferred aluminium oxide that uses, and gives improved selectivity simultaneously.As the wolframic acid caesium (Cs that improves on the catalyst 2WO 4) concentration the time, only obtain optionally to improve and active simultaneously the reduction, yet unexpectedly find, when increasing W content with respect to alkali metal content, selectivity is further enhanced simultaneously that activity has also improved.According to the present invention, under the very high useful load of co-catalyst, can obtain excellent activity, and unlike prior art known activity of such catalysts reduce.In addition, also find and accurately to regulate activity of such catalysts and selectivity by the ratio and the alkali-metal selection of alkali metal-tungsten.When using alkali-metal mixture, can also use cheap metal at least in part, for example potassium or sodium replace more expensive relatively metal for example caesium or rubidium, and can not damage activity of such catalysts or selectivity.
Use is the catalyst of loaded catalyst form, wherein with catalytic active substance dipping surface; Or use the catalyst of the catalyst mode be coating, wherein the mixture with catalytic active substance and carrier material surrounds preferred inert core.In addition, can use extrudate or mechanograph, wherein catalytic active substance mixes with the powder carrier material and then reshapes or with this powder carrier material soaking.Employed carrier material is known inorganic oxide compound, for example SiO 2, TiO 2, ZrO 2And preferred so-called activated alumina.This material has about 10-400m 2The high-specific surface area of/g, and mainly by the oxide of the transition series of the crystalline phase of aluminium oxide form (for example referring to Ullmann ' s Encyclopaedia of IndustrialChemistry of 1985, Vol.A1, p.561-562).These transition oxide comprise γ-, δ-, η-, κ-, χ-and θ-aluminium oxide.When aluminium oxide being heated to more than 1100 ℃, all these crystalline phases all change into heat-staple Alpha-alumina.Activated alumina is sold with different qualities and supply form and is used for catalytic applications.By particle diameter is that 1-5mm, specific area are 180-400m 2/ g, total pore size volume are that 0.3-1.2ml/g and bulk density are that the carrier formed body that the graininess of 300-900g/l or the aluminium oxide extruded are formed is particularly suitable for preparing loaded catalyst.For the object of the invention, preferably use specific area greater than 200m 2The aluminium oxide of/g, this is because finally the catalytic activity of catalyst is along with the surface area increase and the increase slightly of aluminium oxide.Use is this material of powdery, is preferred for preparing catalyst, extrudate or the mechanograph of coating.
The steep water solution that is used to apply co-catalyst can be by plain mode by water-soluble alkali and tungsten compound, especially by wolframic acid (H 2WO 4) and the alkali metal hydroxide preparation., for example wolframic acid is suspended in the water for this reason, and adds alkali and heating and allow its dissolving.Equally with alkali metal hydroxide or another kind of alkali metal salt is water-soluble and combine with the solution (co-catalyst solution) of wolframic acid.Also can favourable use be the alkali metal salt that its anion can be removed fully by heat treatment, for example nitrate, formates, oxalates, acetate or carbonate.Inorganic and organic base be applicable to the pH value be 8 to 14 this is solution-stabilized.It is preferred that the catalyst that obtains after the dipping is carried out the alkali that final heat treatment can remove it fully.These alkali preferably include ammonium hydroxide and organic base, especially amine.Compared with prior art, when preparation steep water solution, the mol ratio of alkali metal and tungsten is selected in such a way, promptly is 2 to 1 wolframic acid caesium (Cs with the ratio of alkali metal/tungsten 2WO 4) or potassium tungstate (K 2WO 4) opposite, there is more a high proportion of tungsten, promptly alkali metal and the ratio of tungsten is less than 2 to 1, especially＜1.9: 1 to 0.9: 1.Compare with known catalyst, this makes catalyst of the present invention have the activity and the selectivity of obvious increase, and is still like this when especially the ratio of hydrogen sulfide and methyl alcohol is low in reacting gas.
When the mixture that uses with the partially mixed tungstates of alkali metal, they preferably two kinds of different alkali metal in the periodic table of elements and ratio between 0.01: 1.0 and 1.0: 1.0.In this case, preferably will conversely relative more expensive alkali metal be reduced to such degree simultaneously, activity of such catalysts or selectivity deterioration will not promptly take place than cheap alkali-metal ratio increase.
About the coating of co-catalyst solution, can use various dipping techniques, for example soak dipping, spraying dipping, vacuum impregnation and pore volume impregnation, and also can flood repeatedly.Under the situation that is mechanograph, selected dipping method must make the required useful load of co-catalyst apply on entire cross section with good homogeneous.
Preferably by a step or two steps this co-catalyst solution is coated on the formed body by spraying or vacuum impregnation.In the spraying dipping, give the spraying of carrier formed body with steep water solution.In vacuum impregnation, use vavuum pump in the container of formed body is housed, to produce decompression.To open towards the hose coupling of steep water solution, and solution is sucked in the container up to the whole bed (bed) of formed body be covered by solution.After dipping 0.2-2 hour, the solution that is not absorbed by material is discharged or pours out.
Made the initial concentration gradient on the cross section of formed body reach balance basically by at room temperature predrying 1-10 hour.Therefore, the uniformity of the dipping on the catalyst granules cross section is improved.Preferably with the catalyst precarsor that obtained at 100-200 ℃, be preferably 100-140 ℃ dry 1-10 hour down, to remove residual moisture.At 300-600 ℃, be preferably 420-480 ℃ and calcined 1-20 hour down then, be preferably 1-5 hour.This is fixed on co-catalyst on the aluminium oxide, and makes the alkali in the dipping solution take place to decompose and be removed.Randomly, air-flow can flow through the bed of the carrier formed body of catalyst precarsor during predrying, dry and calcining, and removing of residual moisture and decomposition gas is improved.
Also can be by a plurality of stages especially two stage dip forming bodies.
In a preferred embodiment, therefore employed solution comprise 1/3rd to 2/3rds of alkali metal and tungsten compound expectation total amount in the phase I.
When this process has a plurality of stages (but at least two stages), the precursor of randomly not calcining in the first step to be obtained.
In addition, in second stage, carry out and the described identical dipping of a terrace work, drying and calcination procedure.
Especially when needing high useful load and/or when the limited solubility of catalyst mixture, make that can not reach useful load with a step time, it is feasible that this multistage floods.
Also can (give the spraying of carrier formed body repeatedly with dipping solution during the step a) of claim 11 in dip operation, and between these treatment steps, in each case, the part of removing residual moisture under up to 120 ℃ temperature is proceeded step b then.
In the Preparation of catalysts that applies, can before or after applying, accept calcining as the powder to be coated of coating.For example, can be according to EP-B-0 068 1 93 these class catalyst of preparation.Same in the preparation of extrudate or mechanograph, also can before reshaping and/or afterwards, calcine.
The specific embodiment
Embodiment
Embodiment 1 (Comparative Examples)
By the wolframic acid caesium (CS of vacuum impregnation with 21.0 weight % 2.0WO 4) dipping 150 gram aluminium oxide I.For this reason, detailed process is as follows:
For preparing this dipping solution, 55.7 gram wolframic acids are suspended in the 44.5 gram water, and the ammonia solution by adding 111.4 grams 25% and be heated to 50 ℃ and make its dissolving.With 74.6 gram Cs (OH) H 2O is dissolved in the 37.3 gram water, and mixes with first solution.In being arranged, the beaker of lid stirred this solution 48 hours subsequently.Afterwards, replenish the volume of this solution to 234 milliliter with 25 gram water.
At first aluminium oxide is packed in the glass container that is evacuated to 150 millibars.By opening stopper, in this glass container that vacuumizes of this dipping solution inspiration, be coated with this solution up to the whole bed of formed body.After the ventilation of 15 minutes stand-by period and this glass container, the solution refluence that will not have oxidized aluminium to absorb is flashed back in the cup.Aluminium oxide has absorbed the dipping solution of 79ml.
With this particle at room temperature in air-flow dry 1 hour, and removed residual moisture down in dry 3 hours at 120 ℃ subsequently.Then, 455 ℃ of following calcining particles 3 hours.
Embodiment 2 (Comparative Examples)
With being mounted with 26.3% wolframic acid caesium (Cs 2.0WO 4) aluminium oxide repeat Comparative Examples 1.
Embodiment 3 (Comparative Examples)
Repeat Comparative Examples 1, wherein adopt to be mounted with 19.6% potassium tungstate (K 2.0WO 4) aluminium oxide, use KOH replaced C s (OH) H 2O.
Embodiment 4
Adopt the co-catalyst (K that adds up to 26.7 weight % by vacuum impregnation 1.6WO y) by the two-stage dipping 150g aluminium oxide (Spheralite 501A) is flooded.Detailed process is as follows:
64.5 gram wolframic acids are suspended in the 50.7 gram water, and make its dissolving by adding 126.9 gram 25% ammonia solutions and being heated to 50 ℃.22.8g KOH is dissolved in the 11.5g water, and mixes with first solution.In being arranged, the beaker of lid stirred this solution 48 hours subsequently.Afterwards, replenish the volume of this solution to 234 milliliter with 39 gram water.At first aluminium oxide is packed in the glass container that is evacuated to 150 millibars.By opening stopper, this maceration extract is sucked, be coated with this solution up to the whole bed of mechanograph.After the ventilation of 15 minutes stand-by period and this glass container, the flow of solution that does not have oxidized aluminium to absorb is flashed back in the cup.Aluminium oxide has absorbed the 76ml dipping solution.Subsequently, with at room temperature dry 1 hour of this particle and 120 ℃ dry 3 hours down, and 455 ℃ of calcinings 3 hours down.
In order to carry out second dipping, identical dipping solution in preparation and the first step and is coated to the catalyst that has loaded that derives from first step by vacuum impregnation in the same way.Like this, at room temperature dry 1 hour once more, then following dry 3 hours at 120 ℃.At last, under air, calcined this catalyst granules 4 hours down at 455 ℃.
Embodiment 5
Adopt the co-catalyst (Rb that adds up to 30.1 weight % by vacuum impregnation 0.9WO y) by the two-stage dipping 150g aluminium oxide (Spheralite 501A) is flooded.Detailed process is as follows:
59.0 gram wolframic acids are suspended in the 48.3 gram water, and make its dissolving by adding 110.7 gram 25% ammonia solutions and being heated to 50 ℃.41.5g RbOH is dissolved in the 17.5g water, and mixes with first solution.In being arranged, the beaker of lid stirred this solution 48 hours subsequently.Afterwards, replenish the volume of this solution to 234 milliliter with 25 gram water.At first aluminium oxide is packed in the glass container that is evacuated to 150 millibars.By opening stopper, the whole bed that this maceration extract is sucked up to mechanograph is coated with this solution.After the ventilation of 15 minutes stand-by period and this glass container, do not have in the solution flow back into beaker of oxidized aluminium absorption.Aluminium oxide has absorbed the 75ml dipping solution.Subsequently, with at room temperature dry 1 hour of this particle and 120 ℃ dry 3 hours down, and 455 ℃ of calcinings 3 hours down.
In order to carry out second dipping, identical dipping solution in preparation and the first step and is coated to the catalyst that has loaded that derives from first step by vacuum impregnation in the same way.Like this, at room temperature dry 1 hour once more, then following dry 3 hours at 120 ℃.At last, under air, calcined this catalyst granules 4 hours down at 455 ℃.
Embodiment 6
Adopt the co-catalyst (K that adds up to 29.4 weight % by vacuum impregnation 0.7Cs 0.7WO y) by the two-stage dipping 150g aluminium oxide (Spheralite 501A) is flooded.Detailed process is as follows:
61.3 gram wolframic acids are suspended in the 49.1 gram water, and make its dissolving by adding 122.7 gram 25% ammonia solutions and being heated to 50 ℃.With 9.8 gram KOH and 29.0g Cs (OH) H 2O is dissolved in the 14.5 gram water, and mixes with first solution.In being arranged, the beaker of lid stirred this solution 48 hours subsequently.Afterwards, replenish the volume of this solution to 234 milliliter with 47 gram water.At first aluminium oxide is packed in the glass container that is evacuated to 150 millibars.By opening stopper, the whole bed that this maceration extract is sucked up to mechanograph is coated with this solution.After the ventilation of 15 minutes stand-by period and this glass container, the flow of solution that does not have oxidized aluminium to absorb is flashed back in the cup.Aluminium oxide has absorbed the 75ml dipping solution.Subsequently, with at room temperature dry 1 hour of this particle and 120 ℃ dry 3 hours down, and 455 ℃ of calcinings 3 hours down.
In order to carry out second dipping, identical dipping solution in preparation and the first step and is coated to the catalyst that has loaded that derives from first step by vacuum impregnation in the same way.Like this, at room temperature dry 1 hour once more, then following dry 3 hours at 120 ℃.At last, under air, calcined this catalyst granules 4 hours down at 455 ℃.
Embodiment 7
Adopt the co-catalyst (Na that adds up to 31.0 weight % by vacuum impregnation 0.3Cs 1.1WO y) by the two-stage dipping 150g aluminium oxide (Spheralite 501A) is flooded.Detailed process is as follows:
61.1 gram wolframic acids are suspended in the 48.9 gram water, and make its dissolving by adding 122.1 gram 25% ammonia solutions and being heated to 50 ℃.With 3.2 gram NaOH and 44.6g Cs (OH) H 2O is dissolved in the 22.3 gram water, and mixes with first solution.In being arranged, the beaker of lid stirred this solution 48 hours subsequently.Afterwards, replenish the volume of this solution to 234 milliliter with 40 gram water.At first aluminium oxide is packed in the glass container that is evacuated to 150 millibars.By opening stopper, the whole bed that this maceration extract is sucked up to mechanograph is coated with this solution.After the ventilation of 15 minutes stand-by period and this glass container, the flow of solution that does not have aluminium oxide to absorb is flashed back in the cup.Aluminium oxide has absorbed the 74ml dipping solution.Subsequently, with at room temperature dry 1 hour of this particle and 120 ℃ dry 3 hours down, and 455 ℃ of calcinings 3 hours down.
In order to carry out second dipping, identical dipping solution in preparation and the first step and is coated to the catalyst that has loaded that derives from first step by vacuum impregnation in the same way.Like this, at room temperature dry 1 hour once more, then following dry 3 hours at 120 ℃.At last, under air, calcined this catalyst granules 4 hours down at 455 ℃.
Embodiment 8 (purposes embodiment)
In by hydrogen sulfide and methyl alcohol synthesis of methyl mercaptan about the performance data detecting catalyst of catalyst.
At internal diameter is that 18mm and length are to synthesize in the stainless steel tube of 500mm.In each case, by the inert bed of glass marble the 76ml catalyst bed is fixed on the two sides of reaction tube.The chuck that use comprises deep fat is heated to about 320 ℃ reaction temperature with this reaction tube.
Experiment condition is following listed:
GHSV:1300h -1(based on standard conditions)
LHSV:0.84h -1(based on liquid MeOH)
Reaction temperature: 320 ℃
Mass ratio
H 2S/MeOH：1.9
Pressure: 9 crust
The reactant mixture that comprises product methyl mercaptan, dimethyl sulfide and dimethyl ether and comprise unconverted initiation material methyl alcohol and hydrogen sulfide by online gc analysis.
When in this catalyst, partly increasing the tungsten part, can see that active obvious increase obtains improved selectivity simultaneously with respect to alkali metal.Compared with prior art, this causes the productive rate up to 10% to increase.Can allow selectivity be increased to by regulating alkali metal-tungstates ratio, and conversion of methanol increase up to about 96.5%.In the commercial scale of methyl mercaptan was synthetic, this had also realized the sizable cost savings in reaction product isolated aspect from unconverted methyl alcohol and accessory substance.
In addition, the result of embodiment 4 to 7 shows: in order optionally to regulate activity of such catalysts and selectivity or for the cost that saves material, can reciprocally exchange the alkali metal of at least a portion in catalyst to be synthetic.
Table 1: experimental result
Catalyst Alkali metal Alkali metal: the mol ratio of tungsten Useful load [weight %] Methanol conversion [%] Selectivity [%] Productive rate [%]
CE1 Cs 2∶1 21.0 82.4 93.3 76.9
CE2 Cs 2∶1 26.3 79.5 94.7 75.2
CE3 K 2∶1 19.6 76.0 95.2 72.4
E4 *) K 1.6∶1 26.7 85.6 95.1 81.4
E5 *) Rb 0.9∶1 30.1 73.2 96.6 70.7
E6 *) K，Cs 1.4∶1 29.4 88.5 95.4 84.4
E7 *) Na，Cs 1.4∶1 31.0 88.4 95.8 84.7
CE1: according to the catalyst of Comparative Examples 1
*)The multistage dipping

Claims (26)

1. the catalyst that comprises the catalytic activity tungstates, this catalytic activity tungstates comprises at least a chemically combined alkali metal and tungsten, and wherein the mol ratio of alkali metal and tungsten is＜2: 1, and caesium only combines existence with other alkali metal.
2. according to the catalytic activity tungstates of claim 1, it comprises at least two kinds of alkali metal and tungsten, and the mol ratio of wherein said alkali-metal summation and tungsten is＜2: 1.
3. according to the catalyst of claim 1 and 2, it comprises the catalyst of coating, wherein with described catalytic activity tungstates coated carrier nuclear, perhaps examines with the carrier material coated carrier of this tungstates dipping.
4. according to the catalyst of claim 1 and 2, wherein will process to produce unsupported catalyst with the described carrier material of described catalytic activity tungstates dipping.
5. according to the catalyst of claim 1 and 2, wherein use the surface of the catalytic activity oxidising composition impregnated carrier formed body of being made up of alkali metal and tungsten, wherein the mol ratio of alkali metal and tungsten is＜2: 1.
6. according to the catalyst of claim 1-5, it is characterized in that the mol ratio of alkali metal and tungsten is＜2: 1 to 0.9: 1 in the described tungstates.
7. according to the catalyst of claim 6, the scope that it is characterized in that described ratio is 1.9: 1 to 1: 1.
8. according to the catalyst of claim 1-5, it is characterized in that described oxidising composition is corresponding to general formula
A xWO y
Wherein,
A: be at least a alkali metal (caesium only combines with other alkali metal and exists)
X: be 0.9 to＜2
Y: be 3.4 to＜4.
9. according to one or multinomial catalyst among the claim 1-8, it is characterized in that it comprises 8-45 weight %, the described tungstates of preferred 20-36 weight %.
10. according to one or multinomial catalyst among the claim 1-9, it is characterized in that described carrier formed body or described carrier material are made of the inorganic oxide compound.
11., be characterised in that described carrier formed body or described carrier material are by aluminium oxide (Al according to the catalyst of claim 10 2O 3) constitute.
12., it is characterized in that described carrier material has 180-400m according to the catalyst of claim 10 2The total pore size volume of the specific area of/g (BET) and 0.3-1.2ml/g.
13., it is characterized in that described alkali metal is potassium according to the catalyst of claim 1 and 3-12.
14., it is characterized in that described alkali metal is rubidium according to the catalyst of claim 1 and 3-12.
15., it is characterized in that described alkali metal is potassium and caesium according to the catalyst of claim 2-12.
16., it is characterized in that described alkali metal is sodium and caesium according to the catalyst of claim 2-12.
17., it is characterized in that described alkali metal is rubidium and caesium according to the catalyst of claim 2-12.
18., it is characterized in that described alkali metal is sodium and potassium according to the catalyst of claim 2-9.
19., it is characterized in that described alkali metal is rubidium and potassium according to the catalyst of claim 2-12.
20. comprise the Preparation of catalysts method of alkali tungstates, wherein carry out following method step:
A) with solution impregnating carrier formed body or carrier material, this aqueous solution comprises soluble alkali metal and tungsten compound with the mol ratio of required alkali metal/tungsten,
It is b) at room temperature that the impregnated formed body of gained or carrier material (catalyst precarsor) in small, broken bits is predrying,
C) randomly 100-200 ℃ down dry removing residual moisture,
D) subsequently 300-600 ℃ temperature lower calcination 2-10 hour and
E) obtain loaded catalyst or impregnated carrier material in small, broken bits, wherein generally consist of A xWO yThe content of co-catalyst be 8-45 weight %, be preferably 15-36 weight %, wherein A, x and y are separately as surface defined and subsequently
F) examine or extrude and suppress will described impregnated carrier material in small, broken bits under the situation of adding known auxiliary agent suspending and be coated to inert carrier.
21., it is characterized in that repeating step a-c at least and optional d once according to the method for claim 20.
22. the method according to claim 20 is characterized in that, under the situation of repeated impregnations, at first the dipping solution of Shi Yonging comprise alkali metal and tungsten the expectation total amount 1/3rd to 2/3rds.
23. according to the method for claim 20, it is characterized in that giving the spraying of described carrier formed body or carrier material repeatedly, and under up to 120 ℃ temperature, removing residual moisture between these treatment steps, carry out treatment step b then) with described dipping solution.
24., it is characterized in that after described impregnated carrier material is coated to described nuclear or after extruding or suppressing, described catalyst being carried out heat treated according to the method for claim 20.
25. the preparation method of alkyl hydrosulfide is included in and allows alkanol and hydrogen sulfide reaction under the existence according to the catalyst of claim 1-19.
26., be used for preparing methyl mercaptan by allowing methyl alcohol and hydrogen sulfide react according to the method for claim 25.
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